US20040157107A1 - Catalyst paste composition for electrode - Google Patents
Catalyst paste composition for electrode Download PDFInfo
- Publication number
- US20040157107A1 US20040157107A1 US10/483,421 US48342104A US2004157107A1 US 20040157107 A1 US20040157107 A1 US 20040157107A1 US 48342104 A US48342104 A US 48342104A US 2004157107 A1 US2004157107 A1 US 2004157107A1
- Authority
- US
- United States
- Prior art keywords
- sulfonated
- polymer
- paste composition
- catalyst paste
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a catalyst paste composition for making electrode layers of fuel cells and the like.
- Fuel cells are generally manufactured with electrode layers and a proton conductive layer.
- the electrode layers used in fuel cells are conventionally produced by applying a catalyst paste that contains carbon supporting a hydrogen reduction catalyst, on carbon paper and heat treating the resultant coating.
- the present invention has an object of providing a catalyst paste composition for the making of electrodes that has a uniform dispersion condition of carbon supporting a hydrogen reduction catalyst and is excellent in storage stability.
- the invention provides the following:
- a catalyst paste composition for making electrodes comprising a carbon black supporting a hydrogen reduction catalyst, an electrolyte, a water-soluble sulfonated polymer and a solvent.
- the sulfonated conjugated diene polymer is at least one polymer selected from a sulfonated polybutadiene, a sulfonated polyisoprene, a sulfonated styrene/butadiene copolymer and a sulfonated styrene/isoprene copolymer.
- the catalyst paste composition for making electrodes according to the invention contains a carbon black supporting a hydrogen reduction catalyst, an electrolyte, a water-soluble sulfonated polymer and a solvent.
- the hydrogen reduction catalyst for use in the invention is preferably a noble metal catalyst, such as platinum, palladium, gold, ruthenium or iridium.
- the hydrogen reduction catalyst may contain two or more such elements; that is, alloys and mixtures of these noble metal catalysts are also available.
- carbon black in the invention oil furnace blacks, channel blacks, lamp blacks, thermal blacks and acetylene blacks are preferable due to their good electron conductivities and large specific surface areas.
- the oil furnace blacks include those carbon blacks commercially available under the trademarks of VULCAN XC-72, VULCAN P, BLACK PEARLS 880, BLACK PEARLS 1100, BLACK PEARLS 1300, BLACK PEARLS 2000, REGAL 400 (all available from Cabot Corporation), KETJENBLACK EC (available from Lion Corporation), and product Nos. 3150 and 3250 of Mitsubishi Chemical Corporation.
- the acetylene blacks include DENKA BLACKTM (available from Denki Kagaku Kogyo K.K.).
- These carbon materials may be in the form of particles or fibers.
- the electrolyte for use in the invention is preferably a polymer having proton exchange groups for enhancing the proton conductivity of the catalyst layer.
- the proton exchange groups in the polymer include sulfonic groups, carboxylic groups and phosphoric groups, but are not particularly limited thereto.
- the polymer with proton exchange groups may be selected without limitation, a proton-exchange polymer composed of a fluoroalkyl main chain and a fluoroalkyl ether side chain, or a sulfonated polyarylene may be preferably employed.
- fluorine-containing polymers, ethylene or styrene polymers, copolymers and blends thereof that contain the proton exchange groups are also available.
- the polymer having proton exchange groups used herein as the electrolyte is insoluble in water.
- the water-soluble sulfonated polymer for use in the invention may be obtained by sulfonating a base polymer resulting from polymerization of one or both of a diene monomer and an aromatic vinyl monomer as essential component(s).
- the diene monomers for synthesis of the base polymer include conjugated or non-conjugated, aliphatic or alicyclic dienes of 4 to 9 carbon atoms that may have a branch, such as 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene,
- conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene and 1,3-cyclopentadiene are preferable.
- the aromatic vinyl monomers for synthesis of the base polymer include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene and vinyl naphthalene.
- the aforesaid monomer(s) can be (co)polymerized in the presence of a radical or anionic polymerization initiator optionally with use of a known solvent.
- the radical polymerization initiators include hydrogen peroxide, benzoyl peroxide and azobisisobutyronitrile.
- the anionic polymerization initiators include n-butyl lithium, sodium naphthalene and sodium metal.
- the base polymer may be sulfonated after part of its residual double bonds has been hydrogenated.
- a common hydrogenation catalyst may be employed.
- JP-A-5/222115 describes hydrogenation catalysts and methods.
- the hydrogenation and sulfonation of the base (co)polymer may be carried out in the order named or the reversed order. The sulfonation method will be described later.
- Exemplary base polymers include isoprene homopolymers, butadiene homopolymers, isoprene/styrene random copolymers, isoprene/styrene block copolymers, styrene/isoprene/styrene block terpolymers, styrene/butadiene random copolymers, styrene/butadiene block copolymers, styrene/butadiene/styrene block copolymers, hydrogenated products of these (co)polymers, and ethylene/propylene/diene terpolymers.
- conjugated diene polymers and the aromatic polymers are preferred, and polybutadiene, polyisoprene, styrene/butadiene copolymers and styrene/isoprene copolymers are more preferred.
- the base polymer or hydrogenated base polymer will range in weight-average molecular weight (Mw) in terms of polystyrene from 3,000 to 1,000,000, more preferably from 5,000 to 500,000, and particularly preferably from 10,000 to 400,000.
- Mw weight-average molecular weight
- the weight-average molecular weight within this range will allow the resultant sulfonated polymer to fully function as a dispersant.
- the sulfonation of the base polymer may be carried out by a known method.
- the water-soluble sulfonated polymer may be obtained by a method described in Shin Jikken Kagaku Kouza (Courses in Experimental Chemistry, vol. 14 III, P.1773, edited by The Chemical Society of Japan) or in JP-A-2/227403.
- the water-soluble sulfonated polymer will contain the sulfonic group in a proportion of not less than 1.5 mmol/g, and more preferably not less than 2 mmol/g.
- the sulfonic group content of less than 1.5 mmol/g may lead to insufficient hydrophilicity, ion trapping properties and other functions, and will also make the polymer less soluble in water so that the coating with an aqueous solvent becomes infeasible.
- the solvent for use in the invention essentially contains water (10-100 wt % of the solvent) and optionally an organic solvent (0-90 wt % of the solvent).
- the organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol and 2-propanol; cyclic ethers such as furan, tetrahydrofuran and dioxane; and ketones such as acetone. These organic solvents may be used singly or in combination of two or more kinds.
- the alcohols are particularly preferable in view of enhancing dispersion condition of the resultant paste.
- the catalyst paste composition for electrodes will contain:
- the catalyst paste composition may be produced by mixing the aforesaid components in a predetermined proportion and kneading the mixture by a common procedure.
- the catalyst paste composition may be applied on an electrode substrate or a proton conductive layer to form an electrode catalyst layer.
- the application methods include brushing, brush coating, bar coating, knife coating, screen printing and spray coating.
- the paste composition may be applied on a substrate (transfer substrate) and thereafter the thus-formed electrode catalyst layer may be transferred onto an electrode substrate or a proton conductive layer.
- the transfer substrate may be a polytetrafluoroethylene (PTFE) sheet or a glass or metal plate whose surface has been treated with a releasing agent.
- PTFE polytetrafluoroethylene
- the electrode substrate for use in the invention is not particularly limited and may be selected from those electrode substrates generally used in fuel cells.
- Examples thereof include porous conductive sheets mainly composed of conductive substances.
- the conductive substances include calcined polyacrylonitriles, calcined pitches, carbon materials such as graphites and expanded graphites, stainless steel, molybdenum and titanium.
- the conductive substances may exist in the form of fibers or particles, but are not limited thereto. Fibrous conductive inorganic substances (inorganic conductive fibers), particularly carbon fibers, are preferable.
- the porous conductive sheets made of such inorganic conductive fibers may be woven or nonwoven fabrics.
- the woven fabrics may be, although not particularly limited to, plain fabrics, twill fabrics, satin fabrics, designed fabrics and figured fabrics.
- the nonwoven fabrics may be, although not particularly limited to, felted nonwoven fabrics, needle punched nonwoven fabrics, spunbonded nonwoven fabrics, water jet punched nonwoven fabrics and meltblown nonwoven fabrics. Knitted fabrics are also usable. These fabrics, particularly when using carbon fibers, are preferably woven fabrics obtained through carbonization or graphitization of plain fabrics of flame-resistant spun yarns, or nonwoven fabrics obtained through carbonization or graphitization of needle punched or water jet punched nonwoven fabrics of flame-resistant yarns, or nonwoven mats obtained by papermaking technique for flame-resistant yarns, carbonized yarns or graphitized yarns.
- carbon paper carbon paper TGP series and SO series (available from Toray Industries, Inc.) and carbon cloths produced by E-TEK may be preferably used.
- conductive particles such as carbon blacks, or conductive fibers such as carbon fibers may be incorporated in the porous conductive sheet used in the invention. The incorporation is advantageous in that such conductive materials play an auxiliary roll to provide a higher conductivity. It will be appreciated that the auxiliary conductive materials are not limited to those listed above.
- platinum-supporting carbon particles (trade name: VULCAN XC-72R carbon available from ElectroChem, Inc., Pt content: 20 wt %);
- the catalyst paste compositions were separately applied on Teflon-treated carbon paper (a product of Toray Industries, Inc.) with use of a doctor blade.
- the resultant coatings were dried in a hot oven at 80° C. for 1 hour. The formed layers were observed for the presence of cissing and particle flocculation.
Abstract
Description
- The present invention relates to a catalyst paste composition for making electrode layers of fuel cells and the like.
- Fuel cells are generally manufactured with electrode layers and a proton conductive layer. The electrode layers used in fuel cells are conventionally produced by applying a catalyst paste that contains carbon supporting a hydrogen reduction catalyst, on carbon paper and heat treating the resultant coating.
- However, it has been a problem with those electrode catalyst pastes that the carbon supporting a hydrogen reduction catalyst per se cannot be dispersed uniformly within a water-containing solvent. Mechanical mixing or a similar treatment can produce only a temporary effect, and the paste cannot maintain uniformity until applied on carbon paper so that the resulting electrode layer will be nonuniform.
- As such, there has been a demand for a catalyst paste for electrodes production in which the carbon supporting a hydrogen reduction catalyst has been dispersed uniformly and with excellent storage stability.
- In consideration of the above circumstances, the present invention has an object of providing a catalyst paste composition for the making of electrodes that has a uniform dispersion condition of carbon supporting a hydrogen reduction catalyst and is excellent in storage stability.
- To achieve the aforesaid object, the invention provides the following:
- (1) A catalyst paste composition for making electrodes, comprising a carbon black supporting a hydrogen reduction catalyst, an electrolyte, a water-soluble sulfonated polymer and a solvent.
- (2) The catalyst paste composition as described in (1), wherein the water-soluble sulfonated polymer is a sulfonated conjugated diene polymer or a sulfonated aromatic polymer.
- (3) The catalyst paste composition as described in (2), wherein the sulfonated conjugated diene polymer is at least one polymer selected from a sulfonated polybutadiene, a sulfonated polyisoprene, a sulfonated styrene/butadiene copolymer and a sulfonated styrene/isoprene copolymer.
- (4) The catalyst paste composition as described in (1), wherein the electrolyte is a perfluorohydrocarbon-based sulfonic acid polymer.
- Hereinbelow, the present invention will be described in more detail.
- The catalyst paste composition for making electrodes according to the invention contains a carbon black supporting a hydrogen reduction catalyst, an electrolyte, a water-soluble sulfonated polymer and a solvent.
- Each component used in the catalyst paste composition will be discussed first.
- (Hydrogen Reduction Catalyst)
- The hydrogen reduction catalyst for use in the invention is preferably a noble metal catalyst, such as platinum, palladium, gold, ruthenium or iridium. The hydrogen reduction catalyst may contain two or more such elements; that is, alloys and mixtures of these noble metal catalysts are also available.
- (Carbon Black)
- For use as the carbon black in the invention, oil furnace blacks, channel blacks, lamp blacks, thermal blacks and acetylene blacks are preferable due to their good electron conductivities and large specific surface areas.
- The oil furnace blacks include those carbon blacks commercially available under the trademarks of VULCAN XC-72, VULCAN P, BLACK PEARLS 880, BLACK PEARLS 1100, BLACK PEARLS 1300, BLACK PEARLS 2000, REGAL 400 (all available from Cabot Corporation), KETJENBLACK EC (available from Lion Corporation), and product Nos. 3150 and 3250 of Mitsubishi Chemical Corporation. The acetylene blacks include DENKA BLACK™ (available from Denki Kagaku Kogyo K.K.).
- Furthermore, natural graphites, pitches, cokes, carbon, and synthetic graphites obtained from organic compounds such as polyacrylonitriles, phenolic resins and furan resins, may also be used.
- These carbon materials may be in the form of particles or fibers.
- (Electrolyte)
- The electrolyte for use in the invention is preferably a polymer having proton exchange groups for enhancing the proton conductivity of the catalyst layer. The proton exchange groups in the polymer include sulfonic groups, carboxylic groups and phosphoric groups, but are not particularly limited thereto. Although the polymer with proton exchange groups may be selected without limitation, a proton-exchange polymer composed of a fluoroalkyl main chain and a fluoroalkyl ether side chain, or a sulfonated polyarylene may be preferably employed. Moreover, fluorine-containing polymers, ethylene or styrene polymers, copolymers and blends thereof that contain the proton exchange groups are also available.
- The polymer having proton exchange groups used herein as the electrolyte is insoluble in water.
- (Water-Soluble Sulfonated Polymer)
- The water-soluble sulfonated polymer for use in the invention may be obtained by sulfonating a base polymer resulting from polymerization of one or both of a diene monomer and an aromatic vinyl monomer as essential component(s).
- The diene monomers for synthesis of the base polymer include conjugated or non-conjugated, aliphatic or alicyclic dienes of 4 to 9 carbon atoms that may have a branch, such as 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene, 3,5-heptadiene, cyclopentadiene, dicyclopentadiene and ethylidene norbornene. These may be used singly or in combination of two or more kinds.
- Of these, the conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene and 1,3-cyclopentadiene are preferable.
- The aromatic vinyl monomers for synthesis of the base polymer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene and vinyl naphthalene.
- To obtain the base polymer, the aforesaid monomer(s) can be (co)polymerized in the presence of a radical or anionic polymerization initiator optionally with use of a known solvent. The radical polymerization initiators include hydrogen peroxide, benzoyl peroxide and azobisisobutyronitrile. The anionic polymerization initiators include n-butyl lithium, sodium naphthalene and sodium metal.
- The base polymer may be sulfonated after part of its residual double bonds has been hydrogenated. For this purpose, a common hydrogenation catalyst may be employed. For example, JP-A-5/222115 describes hydrogenation catalysts and methods. The hydrogenation and sulfonation of the base (co)polymer may be carried out in the order named or the reversed order. The sulfonation method will be described later.
- Exemplary base polymers include isoprene homopolymers, butadiene homopolymers, isoprene/styrene random copolymers, isoprene/styrene block copolymers, styrene/isoprene/styrene block terpolymers, styrene/butadiene random copolymers, styrene/butadiene block copolymers, styrene/butadiene/styrene block copolymers, hydrogenated products of these (co)polymers, and ethylene/propylene/diene terpolymers. Of these, the conjugated diene polymers and the aromatic polymers are preferred, and polybutadiene, polyisoprene, styrene/butadiene copolymers and styrene/isoprene copolymers are more preferred.
- Preferably, the base polymer or hydrogenated base polymer will range in weight-average molecular weight (Mw) in terms of polystyrene from 3,000 to 1,000,000, more preferably from 5,000 to 500,000, and particularly preferably from 10,000 to 400,000. The weight-average molecular weight within this range will allow the resultant sulfonated polymer to fully function as a dispersant.
- The sulfonation of the base polymer may be carried out by a known method. For example, the water-soluble sulfonated polymer may be obtained by a method described in Shin Jikken Kagaku Kouza (Courses in Experimental Chemistry, vol. 14 III, P.1773, edited by The Chemical Society of Japan) or in JP-A-2/227403.
- Preferably, the water-soluble sulfonated polymer will contain the sulfonic group in a proportion of not less than 1.5 mmol/g, and more preferably not less than 2 mmol/g. The sulfonic group content of less than 1.5 mmol/g may lead to insufficient hydrophilicity, ion trapping properties and other functions, and will also make the polymer less soluble in water so that the coating with an aqueous solvent becomes infeasible.
- (Solvent)
- The solvent for use in the invention essentially contains water (10-100 wt % of the solvent) and optionally an organic solvent (0-90 wt % of the solvent). The organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol and 2-propanol; cyclic ethers such as furan, tetrahydrofuran and dioxane; and ketones such as acetone. These organic solvents may be used singly or in combination of two or more kinds.
- Of the above organic solvents, the alcohols are particularly preferable in view of enhancing dispersion condition of the resultant paste.
- (Composition)
- Desirably, the catalyst paste composition for electrodes will contain:
- 2 to 20 wt %, preferably 3 to 15 wt % of the carbon black supporting the hydrogen reduction catalyst;
- 3 to 25 wt %, preferably 3 to 15 wt % of the electrolyte;
- 0.1 to 20 wt %, preferably 2 to 20 wt % of the water-soluble sulfonated polymer;
- 10 to 70 wt % of water; and
- 20 to 70 wt % of the organic solvent.
- The catalyst paste composition may be produced by mixing the aforesaid components in a predetermined proportion and kneading the mixture by a common procedure.
- (Application)
- The catalyst paste composition may be applied on an electrode substrate or a proton conductive layer to form an electrode catalyst layer.
- The application methods include brushing, brush coating, bar coating, knife coating, screen printing and spray coating. Alternatively, the paste composition may be applied on a substrate (transfer substrate) and thereafter the thus-formed electrode catalyst layer may be transferred onto an electrode substrate or a proton conductive layer. The transfer substrate may be a polytetrafluoroethylene (PTFE) sheet or a glass or metal plate whose surface has been treated with a releasing agent.
- The electrode substrate for use in the invention is not particularly limited and may be selected from those electrode substrates generally used in fuel cells. Examples thereof include porous conductive sheets mainly composed of conductive substances. The conductive substances include calcined polyacrylonitriles, calcined pitches, carbon materials such as graphites and expanded graphites, stainless steel, molybdenum and titanium. The conductive substances may exist in the form of fibers or particles, but are not limited thereto. Fibrous conductive inorganic substances (inorganic conductive fibers), particularly carbon fibers, are preferable. The porous conductive sheets made of such inorganic conductive fibers may be woven or nonwoven fabrics. The woven fabrics may be, although not particularly limited to, plain fabrics, twill fabrics, satin fabrics, designed fabrics and figured fabrics. The nonwoven fabrics may be, although not particularly limited to, felted nonwoven fabrics, needle punched nonwoven fabrics, spunbonded nonwoven fabrics, water jet punched nonwoven fabrics and meltblown nonwoven fabrics. Knitted fabrics are also usable. These fabrics, particularly when using carbon fibers, are preferably woven fabrics obtained through carbonization or graphitization of plain fabrics of flame-resistant spun yarns, or nonwoven fabrics obtained through carbonization or graphitization of needle punched or water jet punched nonwoven fabrics of flame-resistant yarns, or nonwoven mats obtained by papermaking technique for flame-resistant yarns, carbonized yarns or graphitized yarns. As the carbon paper, carbon paper TGP series and SO series (available from Toray Industries, Inc.) and carbon cloths produced by E-TEK may be preferably used. According to a preferred embodiment of the invention, conductive particles such as carbon blacks, or conductive fibers such as carbon fibers may be incorporated in the porous conductive sheet used in the invention. The incorporation is advantageous in that such conductive materials play an auxiliary roll to provide a higher conductivity. It will be appreciated that the auxiliary conductive materials are not limited to those listed above.
- The present invention will be hereinafter described in detail by the following Example, but it should be construed that the invention is in no way limited thereto.
- A 250 ml plastic bottle was charged with:
- 3.0 g of platinum-supporting carbon particles (trade name: VULCAN XC-72R carbon available from ElectroChem, Inc., Pt content: 20 wt %);
- 50 g of a water-alcohol solution containing 10 wt % of Nafion (trade name, available from DuPont) (water:alcohol=15:85 by weight);
- 10 g of a sulfonated block copolymer of 30 wt % styrene and isoprene (styrene:isoprene=80:20 (by weight), Mn: 20,000, Mw: 30,000, sulfonic group: 2.16 mEq/g); and
- 37.0 g of distilled water.
- After 300 g of zirconia balls (diameter≠1.0 mm) had been added, the mixture was stirred for 1 hour with a paint mixing and conditioning machine (trade name: Heavy Duty Mixer 5410 available from Red Devil Equipment Co.). A catalyst paste composition for making electrodes was thus obtained.
- A 250 ml plastic bottle was charged with:
- 3.0 g of platinum-supporting carbon particles (trade name: VULCAN XC-72R carbon available from DuPont, Pt content: 20 wt %);
- 50 g of a water-alcohol solution containing 10 wt % of Nafion (trade name, available from Aldrich) (water:alcohol=15:85 by weight); and
- 47.0 g of distilled water.
- After 300 g of zirconia balls (diameter≠1.0 mm) had been added, the mixture was stirred for 1 hour with a paint mixing and conditioning machine (trade name: Heavy Duty Mixer 5410 available from Red Devil Equipment Co.). A catalyst paste 20 composition for making electrodes was thus obtained.
- [Evaluation Procedure]
- (Dispersion Condition)
- The dispersion condition resulting after the 1-hour stirring by the paint conditioner and its storage stability (occurrence of carbon particle sedimentation) were observed.
- (Application Properties)
- The catalyst paste compositions were separately applied on Teflon-treated carbon paper (a product of Toray Industries, Inc.) with use of a doctor blade. The resultant coatings were dried in a hot oven at 80° C. for 1 hour. The formed layers were observed for the presence of cissing and particle flocculation.
- The results are shown in Table 1.
TABLE 1 Dispersion Storage Application condition stability properties Example 1 Uniform No particle Uniform dispersion sedimentation application Comparative No fluidity, Instant Application Example 1 solid paste particle impossible sedimentation
Claims (4)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002146620 | 2002-05-21 | ||
JP2002146620A JP4294263B2 (en) | 2002-05-21 | 2002-05-21 | Electrode catalyst paste composition |
PCT/JP2003/006266 WO2003098723A1 (en) | 2002-05-21 | 2003-05-20 | Catalyst paste composition for electrode |
Publications (2)
Publication Number | Publication Date |
---|---|
US20040157107A1 true US20040157107A1 (en) | 2004-08-12 |
US7060748B2 US7060748B2 (en) | 2006-06-13 |
Family
ID=29545141
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/483,421 Expired - Lifetime US7060748B2 (en) | 2002-05-21 | 2003-05-20 | Catalyst paste composition for electrode |
Country Status (6)
Country | Link |
---|---|
US (1) | US7060748B2 (en) |
EP (1) | EP1507301B1 (en) |
JP (1) | JP4294263B2 (en) |
AU (1) | AU2003234934A1 (en) |
DE (1) | DE60330663D1 (en) |
WO (1) | WO2003098723A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3326224B1 (en) | 2015-07-17 | 2019-05-08 | Cabot Corporation | Oxidized carbon blacks and applications for lead acid batteries |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060040045A1 (en) * | 2004-08-18 | 2006-02-23 | Siegfried Limmer | Method of making electrodes for electrochemical fuel cells |
JP2006092926A (en) * | 2004-09-24 | 2006-04-06 | Jsr Corp | Paste composition for electrode and electrode layer manufactured from composition |
CN100531914C (en) * | 2006-08-09 | 2009-08-26 | 华南理工大学 | solid phase reduction preparation method for platinum, carbon catalyst of fuel cell |
JP5004618B2 (en) * | 2007-02-28 | 2012-08-22 | 旭化成イーマテリアルズ株式会社 | Electrolyte composition, catalyst layer, and polymer electrolyte fuel cell |
DE102010018824B4 (en) * | 2010-04-29 | 2021-02-04 | Krones Aktiengesellschaft | Detection of foreign substances in filled bottles |
JP2011258349A (en) * | 2010-06-07 | 2011-12-22 | Daido Gakuen | Film-electrode assembly and solid polymer fuel cell |
JP6241214B2 (en) * | 2013-11-08 | 2017-12-06 | 東洋インキScホールディングス株式会社 | Composition for forming fuel cell electrode and fuel cell using the same |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4255312A (en) * | 1978-03-18 | 1981-03-10 | Nippon Oil Co., Ltd. | Aqueous pigment dispersion used for aqueous coating compositions |
US5135675A (en) * | 1989-07-13 | 1992-08-04 | Lever Brothers Company, Divison Of Conopco, Inc. | Machine dishwashing compositions comprising organic clay and sulfonated polystyrene polymer or copolymer as thickening agents |
US5962169A (en) * | 1992-06-22 | 1999-10-05 | Arizona Board Of Regents | Lithium ion conducting electrolytes |
US20020172850A1 (en) * | 2001-01-19 | 2002-11-21 | Honda Giken Kogyo Kabushiki Kaisha, Jsr Corporation | Polymer electrolyte membrane and solid polymer electrolyte fuel cell using same |
US6492295B2 (en) * | 2000-03-15 | 2002-12-10 | Japan Storage Battery Co., Ltd. | Composite catalyst for solid polymer electrolyte type fuel cell and processes for producing the same |
US6670065B2 (en) * | 2000-09-29 | 2003-12-30 | Hitachi, Ltd. | Solid polymer electrolyte, a membrane using thereof, a solution for coating electrode catalyst, a membrane/electrode assembly, and a fuel cell |
US6818339B1 (en) * | 1999-08-27 | 2004-11-16 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte type fuel cell |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6054230A (en) * | 1994-12-07 | 2000-04-25 | Japan Gore-Tex, Inc. | Ion exchange and electrode assembly for an electrochemical cell |
JP3970390B2 (en) * | 1997-08-22 | 2007-09-05 | 旭化成株式会社 | Membrane-electrode assembly for solid polymer fuel cell |
JP4974403B2 (en) * | 2000-05-31 | 2012-07-11 | 日本ゴア株式会社 | Solid polymer electrolyte fuel cell |
JP2002134119A (en) * | 2000-10-19 | 2002-05-10 | Japan Storage Battery Co Ltd | Fuel cell and electrode for fuel cell |
DE10201691A1 (en) * | 2001-01-19 | 2002-09-05 | Honda Motor Co Ltd | Polymer electrolyte membrane for electrolyte fuel cell, is obtained by subjecting ion-conductive, aromatic polymer membrane having preset water absorption to hot-water treatment |
-
2002
- 2002-05-21 JP JP2002146620A patent/JP4294263B2/en not_active Expired - Fee Related
-
2003
- 2003-05-20 EP EP03752921A patent/EP1507301B1/en not_active Expired - Fee Related
- 2003-05-20 AU AU2003234934A patent/AU2003234934A1/en not_active Abandoned
- 2003-05-20 WO PCT/JP2003/006266 patent/WO2003098723A1/en active Application Filing
- 2003-05-20 DE DE60330663T patent/DE60330663D1/en not_active Expired - Lifetime
- 2003-05-20 US US10/483,421 patent/US7060748B2/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4255312A (en) * | 1978-03-18 | 1981-03-10 | Nippon Oil Co., Ltd. | Aqueous pigment dispersion used for aqueous coating compositions |
US5135675A (en) * | 1989-07-13 | 1992-08-04 | Lever Brothers Company, Divison Of Conopco, Inc. | Machine dishwashing compositions comprising organic clay and sulfonated polystyrene polymer or copolymer as thickening agents |
US5962169A (en) * | 1992-06-22 | 1999-10-05 | Arizona Board Of Regents | Lithium ion conducting electrolytes |
US6818339B1 (en) * | 1999-08-27 | 2004-11-16 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte type fuel cell |
US6492295B2 (en) * | 2000-03-15 | 2002-12-10 | Japan Storage Battery Co., Ltd. | Composite catalyst for solid polymer electrolyte type fuel cell and processes for producing the same |
US6670065B2 (en) * | 2000-09-29 | 2003-12-30 | Hitachi, Ltd. | Solid polymer electrolyte, a membrane using thereof, a solution for coating electrode catalyst, a membrane/electrode assembly, and a fuel cell |
US20020172850A1 (en) * | 2001-01-19 | 2002-11-21 | Honda Giken Kogyo Kabushiki Kaisha, Jsr Corporation | Polymer electrolyte membrane and solid polymer electrolyte fuel cell using same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3326224B1 (en) | 2015-07-17 | 2019-05-08 | Cabot Corporation | Oxidized carbon blacks and applications for lead acid batteries |
Also Published As
Publication number | Publication date |
---|---|
EP1507301B1 (en) | 2009-12-23 |
JP2003338288A (en) | 2003-11-28 |
DE60330663D1 (en) | 2010-02-04 |
AU2003234934A8 (en) | 2003-12-02 |
AU2003234934A1 (en) | 2003-12-02 |
EP1507301A4 (en) | 2008-07-02 |
WO2003098723A1 (en) | 2003-11-27 |
US7060748B2 (en) | 2006-06-13 |
EP1507301A1 (en) | 2005-02-16 |
JP4294263B2 (en) | 2009-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Millington et al. | The effect of materials on proton exchange membrane fuel cell electrode performance | |
CN100403589C (en) | Membrane electrode complex and solid polymer type fuel cell using it | |
CN1974639B (en) | Polymer electrolyte membrane for fuel cell and fuel cell system | |
KR101995527B1 (en) | Reinforced composite membrane for fuel cell and membrane-electrode assembly for fuel cell comprising the same | |
JP4144686B2 (en) | Method for producing polymer electrolyte fuel cell | |
US20090011308A1 (en) | Preparation of Gas Diffusion Layer for Fuel Cell | |
WO2009098982A1 (en) | Membrane-electrode assembly and solid polymer electrolyte fuel cell | |
KR20080090488A (en) | Microporous layer | |
Han et al. | Development of carbon-filled gas diffusion layer for polymer electrolyte fuel cells | |
US7060748B2 (en) | Catalyst paste composition for electrode | |
JP2007115413A (en) | Fuel cell | |
JP2007080726A (en) | Membrane electrode assembly | |
KR100578981B1 (en) | Electrode for fuel cell and the fuel cell system comprising the same | |
DE60314643T2 (en) | PREPARATION OF GAS DIFFUSION ELECTRODES | |
JP4837253B2 (en) | Electrocatalyst ink | |
DE60100543T2 (en) | ANODE STRUCTURE WITH A CARBONATE COMPONENT THAT HAS A LOW CORROSION RESISTANCE | |
EP1503439B1 (en) | Process of producing electrode paste | |
EP1450424B1 (en) | Electrode paste composition | |
DE102013205290B4 (en) | Rubber crack reducing agent in polyelectrolyte membranes | |
CA2423864A1 (en) | Method for operating a fuel cell, polymer-electrolyte membrane fuel cell which works with this method and process for producing it | |
CN113764685A (en) | Preparation method of gas diffusion layer | |
JP2007080725A (en) | Membrane electrode assembly | |
US20040028991A1 (en) | Material for electrode manufacture | |
TWI395365B (en) | A method to manufacture the membrane electrode assembly in air breathing fuel cell | |
KR20220025867A (en) | Methods for producing catalyst coated membranes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: JSR CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HIGAMI, MAKOTO;BESSHO, KEIICHI;REEL/FRAME:015123/0727 Effective date: 20040209 Owner name: HONDA MOTOR CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HIGAMI, MAKOTO;BESSHO, KEIICHI;REEL/FRAME:015123/0727 Effective date: 20040209 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553) Year of fee payment: 12 |